US7047764B2 - Modular LNG process - Google Patents

Modular LNG process Download PDF

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Publication number
US7047764B2
US7047764B2 US10/676,930 US67693003A US7047764B2 US 7047764 B2 US7047764 B2 US 7047764B2 US 67693003 A US67693003 A US 67693003A US 7047764 B2 US7047764 B2 US 7047764B2
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Prior art keywords
light hydrocarbon
hydrocarbon gas
launch train
facilities
liquefaction
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US10/676,930
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US20040118153A1 (en
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Jeffrey H. Sawchuk
Richard Jones, Jr.
Patrick B. Ward
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BP Corp North America Inc
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BP Corp North America Inc
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Assigned to BP CORPORATION NORTH AMERICA INC. reassignment BP CORPORATION NORTH AMERICA INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: WARD, PATRICK B., JONES, RICHARD JR., SAWCHUK, JEFFREY H.
Publication of US20040118153A1 publication Critical patent/US20040118153A1/en
Priority to US11/325,933 priority patent/US7251956B2/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D15/00—Adaptations of machines or engines for special use; Combinations of engines with devices driven thereby
    • F01D15/005—Adaptations for refrigeration plants
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K23/00—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids
    • F01K23/02—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled
    • F01K23/06—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled combustion heat from one cycle heating the fluid in another cycle
    • F01K23/064—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled combustion heat from one cycle heating the fluid in another cycle in combination with an industrial process, e.g. chemical, metallurgical
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K23/00—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids
    • F01K23/02—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled
    • F01K23/06—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled combustion heat from one cycle heating the fluid in another cycle
    • F01K23/10—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled combustion heat from one cycle heating the fluid in another cycle with exhaust fluid of one cycle heating the fluid in another cycle
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02C—GAS-TURBINE PLANTS; AIR INTAKES FOR JET-PROPULSION PLANTS; CONTROLLING FUEL SUPPLY IN AIR-BREATHING JET-PROPULSION PLANTS
    • F02C6/00—Plural gas-turbine plants; Combinations of gas-turbine plants with other apparatus; Adaptations of gas-turbine plants for special use
    • F02C6/04—Gas-turbine plants providing heated or pressurised working fluid for other apparatus, e.g. without mechanical power output
    • F02C6/10—Gas-turbine plants providing heated or pressurised working fluid for other apparatus, e.g. without mechanical power output supplying working fluid to a user, e.g. a chemical process, which returns working fluid to a turbine of the plant
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02C—GAS-TURBINE PLANTS; AIR INTAKES FOR JET-PROPULSION PLANTS; CONTROLLING FUEL SUPPLY IN AIR-BREATHING JET-PROPULSION PLANTS
    • F02C6/00—Plural gas-turbine plants; Combinations of gas-turbine plants with other apparatus; Adaptations of gas-turbine plants for special use
    • F02C6/18—Plural gas-turbine plants; Combinations of gas-turbine plants with other apparatus; Adaptations of gas-turbine plants for special use using the waste heat of gas-turbine plants outside the plants themselves, e.g. gas-turbine power heat plants
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0022—Hydrocarbons, e.g. natural gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0211—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using a multi-component refrigerant [MCR] fluid in a closed vapor compression cycle
    • F25J1/0214—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using a multi-component refrigerant [MCR] fluid in a closed vapor compression cycle as a dual level refrigeration cascade with at least one MCR cycle
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0257—Construction and layout of liquefaction equipments, e.g. valves, machines
    • F25J1/0269—Arrangement of liquefaction units or equipments fulfilling the same process step, e.g. multiple "trains" concept
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0257—Construction and layout of liquefaction equipments, e.g. valves, machines
    • F25J1/0269—Arrangement of liquefaction units or equipments fulfilling the same process step, e.g. multiple "trains" concept
    • F25J1/027—Inter-connecting multiple hot equipments upstream of the cold box
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0257—Construction and layout of liquefaction equipments, e.g. valves, machines
    • F25J1/0274—Retrofitting or revamping of an existing liquefaction unit
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0279—Compression of refrigerant or internal recycle fluid, e.g. kind of compressor, accumulator, suction drum etc.
    • F25J1/0281—Compression of refrigerant or internal recycle fluid, e.g. kind of compressor, accumulator, suction drum etc. characterised by the type of prime driver, e.g. hot gas expander
    • F25J1/0283—Gas turbine as the prime mechanical driver
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0279—Compression of refrigerant or internal recycle fluid, e.g. kind of compressor, accumulator, suction drum etc.
    • F25J1/0294—Multiple compressor casings/strings in parallel, e.g. split arrangement
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2210/00—Working fluids
    • F05D2210/10—Kind or type
    • F05D2210/12—Kind or type gaseous, i.e. compressible
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2220/00—Application
    • F05D2220/70—Application in combination with
    • F05D2220/72—Application in combination with a steam turbine
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2220/00—Application
    • F05D2220/70—Application in combination with
    • F05D2220/76—Application in combination with an electrical generator
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/60—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2220/00—Processes or apparatus involving steps for the removal of impurities
    • F25J2220/60—Separating impurities from natural gas, e.g. mercury, cyclic hydrocarbons
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2220/00—Processes or apparatus involving steps for the removal of impurities
    • F25J2220/60—Separating impurities from natural gas, e.g. mercury, cyclic hydrocarbons
    • F25J2220/64—Separating heavy hydrocarbons, e.g. NGL, LPG, C4+ hydrocarbons or heavy condensates in general
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2220/00—Processes or apparatus involving steps for the removal of impurities
    • F25J2220/60—Separating impurities from natural gas, e.g. mercury, cyclic hydrocarbons
    • F25J2220/66—Separating acid gases, e.g. CO2, SO2, H2S or RSH
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2220/00—Processes or apparatus involving steps for the removal of impurities
    • F25J2220/60—Separating impurities from natural gas, e.g. mercury, cyclic hydrocarbons
    • F25J2220/68—Separating water or hydrates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S62/00—Refrigeration
    • Y10S62/902—Apparatus
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S62/00—Refrigeration
    • Y10S62/902—Apparatus
    • Y10S62/911—Portable

Definitions

  • This invention relates to a method for liquefying variable selected quantities of light hydrocarbon gas to produce liquefied light hydrocarbon gas using plant facilities that comprise an initial light hydrocarbon gas liquefaction launch train with common shared facilities, which may be expanded by adding plant equipment associated with one or more optional expansion phases to the launch train.
  • natural gas may contain condensates that are light gasoline boiling range materials as well as C 3 –C 5 gaseous hydrocarbons and methane.
  • such natural gas also contains undesirably high quantities of water, acid gas compounds such as sulfur compounds, carbon dioxide and the like for liquefaction to produce liquefied light hydrocarbon gases, which typically comprise primarily methane and which are frequently referred to as liquefied natural gas (LNG).
  • acid gas compounds such as sulfur compounds, carbon dioxide and the like for liquefaction to produce liquefied light hydrocarbon gases, which typically comprise primarily methane and which are frequently referred to as liquefied natural gas (LNG).
  • LNG liquefied natural gas
  • the capacity of the liquefaction plant is determined primarily by the available market for the gas, the availability of transportation to the market and the like. Accordingly in many instances it is desirable to increase the capacity of the liquefaction process in incremental stages as the market expands to remain in balance with the available market. Accordingly light hydrocarbon gas liquefaction processes, referred to herein as natural gas liquefaction processes or LNG processes, are typically installed in trains.
  • train refers to a series of vessels capable of, pre-treating and liquefying natural gas. The gas is desirably treated to remove acid gases and water to very low levels prior to charging it to the liquefaction zone.
  • the train also includes compression facilities for compressing the refrigerant required for the refrigeration vessel and the like.
  • the train is an integrated process for producing a selected quantity of liquefied natural gas.
  • industry has expanded plant capacity by adding one or more additional trains (each of which includes its own gas pretreatment equipment, liquefaction equipment, as well as liquefied product transport and storage facilities), as required to meet the available market demand and the like.
  • trains have been previously designed to produce a certain quantity of liquefied product with no future expansion of the train having been considered in the design.
  • FIG. 1 an embodiment of a light hydrocarbon gas liquefaction system and process (train) is schematically shown.
  • the system and process includes a refrigeration cryogenic heat exchanger 15 .
  • compressed refrigerant is supplied to cryogenic heat exchanger 15 by turbines 31 , 33 , 35 , and 37 , which are shaft coupled to refrigerant compressors 32 , 34 , 36 , and 38 , respectfully.
  • High-pressure refrigerant is supplied to compressors 32 and 34 by high-pressure refrigerant lines 61 and 62 . These lines typically return high-pressure refrigerant from cryogenic heat exchanger 15 after it has served its purpose as a refrigerant and has been warmed to a substantially gaseous condition.
  • Compressed high-pressure refrigerant is supplied to cryogenic heat exchanger 15 via lines 63 and 64 .
  • Low-pressure refrigerant is supplied to compressors 36 and 38 by low-pressure refrigerant lines 65 and 66 . These lines typically return low-pressure refrigerant from cryogenic heat exchanger 15 after it has served its purpose as a refrigerant and has been warmed to substantially gaseous condition.
  • Compressed low-pressure refrigerant is supplied to cryogenic heat exchanger 15 via lines 67 and 68 . No significance should be attributed to this except that refrigerants can be produced from compressors 32 , 34 , 36 , and 38 at different pressures if desired and passed to cryogenic heat exchanger 15 at different points in the refrigeration process if desired.
  • the same or different refrigerants can be used in the high-pressure and low-pressure refrigerant loops, as known to those skilled in the art.
  • an inlet light hydrocarbon gas that has desirably been treated to remove acid gases and water is charged to cryogenic heat exchanger 15 via line 59 .
  • the liquefied light hydrocarbon gas product is produced through line 69 .
  • a natural gas or other light hydrocarbon gas stream is introduced to acid gas removal vessel 10 via line 40 .
  • Acid gas regenerator 11 is shown in fluid communication with acid gas removal vessel 10 via lines 41 and 42 .
  • the treated gas is typically recovered from vessel 10 through line 43 .
  • the recovered gases are passed via lines 44 , 45 , and 46 to designated dehydration vessels 20 , 21 , and 22 .
  • vessel 10 is an aqueous amine scrubber, operating as known to those skilled in the art.
  • the aqueous amine may be selected from materials such as digycolanolamine (DGA), diethylamine (DEA), methyldiethanolamine (MDEA), methylethylanolamine (MEA), SULFINOL (trademark of Shell Oil Company), activated methyldiethanolamine (aMDEA), and combinations thereof.
  • DGA digycolanolamine
  • DEA diethylamine
  • MDEA methyldiethanolamine
  • MEA methylethylanolamine
  • SULFINOL trademark of Shell Oil Company
  • activated methyldiethanolamine aMDEA
  • Carbon dioxide is typically removed to levels less than about 60 parts per million (ppm) while sulfur is typically removed to levels less than about 4 ppm through vessels such as acid gas removal vessel 10 .
  • Treated water-saturated gas is recovered from acid gas removal vessel 10 via line 43 where it is passed to dehydration vessels 20 , 21 , and 22 via lines 44 , 45 , and 46 , respectfully. Water is selectively removed through dehydration vessels 20 , 21 , and 22 to produce a dewatered gas in lines 54 , 55 , and 56 .
  • the dehydrated gas from vessels 20 , 21 , and 22 is then combined and passed to cryogenic heat exchanger 15 via line 59 .
  • these dehydration vessels contain an adsorption material such as a molecular sieve, activated alumina, or the like. Such material is effective in removing the water from an inlet gaseous stream to extremely low levels, thus rendering the gaseous stream suitable for liquefaction in cryogenic heat exchanger 15 .
  • three vessels are placed in each train to meet the requirements to dehydrate incoming gas.
  • the process may also use adsorption materials for removal of other contaminants, such as mercury.
  • dehydration vessels 20 , 21 , and 22 two vessels will generally serve to remove the water from its associated feed gas stream, 44 , 45 , or 46 , while one vessel is being regenerated by hot regeneration gas.
  • Such configuration is depicted in FIG. 1 where dehydration vessels 20 and 21 serve to produce relatively water free gas streams 54 and 55 by removing water from inlet gas streams 44 and 45 .
  • Dehydration vessel 22 in the depicted configuration, is being regenerated by hot regeneration gas where the regeneration gas enters the vessel via line 70 and exits via line 71 . All dehydration vessels 20 , 21 , and 22 all have the capability to operate in either dehydration or regeneration mode (though not shown for simplicity), as indicated in FIG. 1 by vessel 22 and process streams 70 and 71 .
  • Typically three vessels are placed in each train to meet the requirements of dehydration the incoming gas.
  • the acid gas removal vessels are readily regenerated as well known to those skilled in the art by a variety of techniques.
  • One commonly used technique is the use of a reboiler on vessel 11 for regeneration.
  • the expense required for these vessels can be reduced by a method for designing an efficient and economical light hydrocarbon gas liquefaction process for the liquefaction of selected quantities of light hydrocarbon gas in an initial launch light hydrocarbon gas liquefaction train and one or more optional subsequent expansion phases to said light hydrocarbon liquefaction train to liquefy additional selected quantities of light hydrocarbon gas up to a selected maximum quantity of light hydrocarbon gas for the process.
  • the method comprises:
  • the launch train including facilities for light hydrocarbon gas pretreatment to remove acid gases and water, refrigerant compression, cryogenic heat exchange, access services, light hydrocarbon gas liquefaction, and liquefied light hydrocarbon gas product storage and shipping;
  • the shared use facilities of the launch train being designed at a size sufficient to liquefy the selected maximum quantity of light hydrocarbon gas for the process either in the launch train as constructed or as constructed in the launch train and expanded in the one or more optional expansion phases to the required capacity.
  • a) constructing a light hydrocarbon gas liquefaction launch train for the liquefaction of a first selected quantity of light hydrocarbon gas including facilities for light hydrocarbon gas pretreatment to remove acid gases and water, refrigerant compression, cryogenic heat exchange, access services, light hydrocarbon gas liquefaction, and liquefied light hydrocarbon gas product storage and shipping;
  • the process includes a light hydrocarbon gas liquefaction launch train to liquefy an initial amount of light hydrocarbon gas and one or more optional subsequent expansion phases to said light hydrocarbon gas liquefaction train to liquefy additional selected quantities of light hydrocarbon gas up to a selected maximum quantity of light hydrocarbon gas for the process.
  • the method comprises:
  • the launch train including facilities for light hydrocarbon gas pretreatment to remove acid gases and water, refrigerant compression, cryogenic heat exchange, access services, light hydrocarbon gas liquefaction, and liquefied light hydrocarbon gas product storage and shipping;
  • the shared use facilities of the launch train being designed at a size sufficient to liquefy the selected maximum quantity of light hydrocarbon gas for the process either in the launch train as constructed or as constructed in the launch train and expanded in the one or more optional expansion phases to the required capacity;
  • the invention also relates to a method for efficiently and economically operating a light hydrocarbon gas liquefaction process for the liquefaction of selected quantities of light hydrocarbon gas.
  • the process includes a light hydrocarbon gas liquefaction launch train to liquefy an initial amount of light hydrocarbon gas and one or more subsequent expansion phases to said light hydrocarbon gas liquefaction train to liquefy additional selected quantities of light hydrocarbon gas up to a selected maximum quantity of light hydrocarbon gas for the process.
  • the method comprises:
  • the launch train including facilities for light hydrocarbon gas pretreatment to remove acid gases and water, refrigerant compression, cryogenic heat exchange, access services, light hydrocarbon gas liquefaction, and liquefied light hydrocarbon gas product storage and shipping;
  • the shared use facilities of the launch train being designed at a size sufficient to liquefy the selected maximum quantity of light hydrocarbon gas for the process either in the launch train as constructed or as constructed in the launch train and expanded in the one or more expansion phases to the required capacity;
  • expansion phases capable of producing liquefied light hydrocarbon gas by use of the shared use facilities in the launch train as constructed in the launch train or as constructed in the launch train and expanded in the one or more expansion phases to the required capacity;
  • FIG. 1 is a schematic diagram of a process for liquefying light hydrocarbon gas using one liquefaction train.
  • FIG. 2 is a schematic diagram of an embodiment of the invention using an acid gas removal facility as a shared use facility where a launch train comprises equipment and associated piping depicted with solid lines and subsequent expansion phases (modules) to the launch train comprise equipment and associated piping depicted by the dashed lines.
  • FIG. 3 is a schematic diagram of an embodiment of the invention using a dehydration facility as a shared use facility where a launch train comprises equipment and associated piping depicted with solid lines and subsequent expansion phases (modules) to the launch train comprise equipment and associated piping depicted by the dashed lines.
  • FIG. 4 is a schematic diagram of an embodiment of a liquefaction facility where a launch train comprises refrigerant compression and cryogenic heat exchange equipment and associated piping depicted with solid lines and subsequent expansion phases (modules) comprise refrigerant compression and cryogenic heat exchange equipment and associated piping depicted by the dashed lines.
  • the present invention provides an improved efficiency and economy in operating a light hydrocarbon gas liquefaction process for the liquefaction of selected quantities of light hydrocarbon gas by use of an initial light hydrocarbon gas liquefaction launch train, and up to a selected maximum quantity of liquefied light hydrocarbon gas using one or more subsequent modular expansion phases by a method comprising the design of such process to include certain facilities which are common to both the initial launch train and subsequent expansion phases.
  • the term “light hydrocarbon gas liquefaction train” or “train” refers to those units and facilities used for pretreatment and post-treatment of the gas feeds to the liquefaction facility as well as the facilities for compressing the refrigerant and the like as shown in FIG. 1 .
  • Such acid gas facilities can include acid gas removal equipment, dehydration equipment, mercury or other contaminant removal equipment, and refrigerant compression and cryogenic heat exchange equipment, and associated piping.
  • Vessels for the removal of acid gases and for dehydration typically include both an absorption vessel and a regenerator vessel to regenerate the media used in the vessel for acid gas removal or for dehydration respectively.
  • an absorption vessel and a regeneration vessel are required in the acid gas removal section. If these facilities are duplicated in each train (as previously practiced within the art) then each train will include an absorption vessel and a regenerator vessel.
  • the train was designed and constructed to include a regenerator for the aqueous amine used in the acid gas absorption vessels of a size sufficient to accommodate additional absorption vessels as required as additional expansions are desired.
  • this equipment is located in an area which is equally accessible or at least accessible to all necessary equipment so that additional acid gas removal vessels can be positioned to serve the launch train and additional expansions and remain in fluid communication with the regenerator vessel for the regeneration and recycling of the aqueous amine solution used for the acid gas absorption.
  • these vessels could be commonly sited with the gas from which the acid gases have been removed being then passed to the appropriate liquefaction facility. This results in the construction of only a single aqueous amine regeneration vessel and permits the construction of only an additional acid gas absorption vessel for each subsequent liquefaction expansion phase.
  • dehydration vessels When dehydration vessels are used three are typically constructed for each train. Two vessels are typically used for adsorption of water with the third being regenerated by hot gases which drive out the water.
  • a plurality of dehydration vessels can be placed together at a common site to dewater the reduced acid gas content gas produced by the removal of the acid gases to produce a dewatered light liquid hydrocarbon gas stream having a reduced acid gas content. It is well known that the regeneration times for such vessels is substantially less than the time required on line for dehydration.
  • Prior practice has been to provide three dehydration vessels for each train so that two vessels are on line while the other vessel is being regenerated.
  • the vessels are located at a common site only one extra vessel needs to be added during an expansion.
  • the single vessel is sufficient since the two vessels which are operative at any given time will operate for long enough to provide time to regenerate the third vessel.
  • the third vessel is regenerated the gas flow from one of the other vessels which may have become spent can be rerouted to the regenerated vessel with the vessel which has become spent then being regenerated.
  • These vessels can be used in groups wherein the number of vessels usable in a group is equal to a number equal to the run time for each vessel divided by the regeneration time to produce a number which is a whole number disregarding any fraction plus one. This number defines the number of vessels which can be used with one additional vessel for regeneration. In the event that the regeneration time is equal to one third of the run time then four vessels can be used to service three trains rather than the six vessels which would normally be constructed according to the prior art. Similarly improvements can be realized in the construction of docking facilities, liquid natural gas storage and shipping facilities, C 3 +hydrocarbon removal facilities and the like.
  • these facilities are produced in a form in the first launch train from which they can be expanded by modular increments or of a size necessary to handle the maximum quantity of light hydrocarbon gas which will be processed through the liquefaction process.
  • Such processes have been expanded by adding trains and as indicated previously by duplicating all the facilities required for each train in each train.
  • shared facilities are used by the first liquefaction launch train and the subsequent modular expansion phases.
  • the initial launch liquefaction train is designed to size the shared equipment of a size capable of handling the maximum capacity expected by the combination of the initial launch train and incremental expansion as modular expansion phases are added to increase capacity. For instance, less than a full amount of compressed refrigerant may be charged in a subsequent modular expansion initially. This permits addition of the expansion phase before a market exists for all of the liquefied natural gas which could be produced through the facility. It also permits ready expansion of this system when the market expands to include a full compressed refrigerant charge to another subsequent modular expansion phase.
  • FIG. 2 illustrates a phased expansion of an acid gas removal unit (AGRU) where the solid lines represent a launch (new or existing) train and the dotted lines represent optional future expansion equipment and associated piping required for a one or two-phase expansion.
  • each train typically contains an acid gas removal vessel 10 and an acid gas regenerator 11 .
  • the facilities required for acid gas removal for the initial launch train and subsequent expansions be arranged in a common area, or at least in reasonable fluid communication in efforts to reduce capital expenditure and improve the overall plant layout. For example, if it is desired to increase the plant throughput, acid gas removal vessel 110 and acid gas regenerator 111 along with associated piping could be installed, thus increasing the throughput of the original AGRU.
  • a further train expansion could be obtained through the addition of acid gas removal vessel 210 and acid gas regenerator 211 along with associated piping.
  • the need for multiple acid gas regenerators could be eliminated by using one acid gas regenerator, which would further reduce the capital expenditure and space (real estate) required by full train expansions previously known in the art.
  • the acid gas regenerator 11 can be sized so that it can handle all of the regeneration requirements for future expansions, thereby eliminating the need for acid gas regenerators 111 and 211 .
  • three acid gas removal vessels 10 , 110 , and 210 are available for use to remove acid gases from inlet gas streams, which are charged via line 40 ′ (forty prime).
  • the inlet gas may be passed via lines 40 , 140 , and 240 to any or all of the acid gas removal vessels 10 , 110 , and 210 .
  • the acid gas removal vessels shown may employ aqueous amine solutions, as known generally in the art, and operate as discussed in connection with FIG. 1 .
  • the gaseous streams having reduced acid gas content are recovered through lines 43 , 143 , and 243 where they combine to create stream 43 ′ (forty-three prime), which then continues through the remainder of the process.
  • the facility could attend to the acid gas removal needs for the launch train and additional expansions with regeneration occurring in the three regeneration vessels 11 , 111 , and 211 , or one appropriately sized regeneration vessel as previously mentioned.
  • the fresh amine is produced via lines 42 , 142 , and 242 and passed into the upper portion of vessels 10 , 110 , and 210 , respectfully.
  • the spent amine is passed via lines 41 , 141 , and 241 to vessels 11 , 111 , and 211 to complete the loop.
  • the fresh amine from the acid gas regeneration vessel carried by one primary line (not shown for simplicity) exiting the lower portion of the regeneration vessel, would be appropriately distributed through lines 42 , 142 , and 242 .
  • the spent amine would leave acid gas removal vessels 10 , 110 , and 210 via lines 41 , 141 , and 241 and combine into one primary line (also not shown) entering the upper portion of the single acid gas regeneration vessel.
  • a regenerated aqueous amine solution is provided to the upper portion of each vessel on a continuous basis with spent amine solution being recovered from the lower portion of the vessel and passed back to regeneration.
  • the vessel must be sized to provide sufficient fresh regenerated aqueous amine to remove the acid gas compounds from the gaseous stream charged to the operating acid gas removal vessels, 10 , 110 , and 210 .
  • the sizing of one regeneration vessel entails little additional expense to provide sufficient regenerating capacity to provide sufficient regenerated amine to service all four of the vessels.
  • additional expansions can be made by simply adding a single acid gas removal contact vessel. So long as significant regeneration capacity exists, the gain in gas throughput is obtained at a considerably reduced capital cost by virtue of requiring only the addition of a single acid gas removal vessel rather than an acid gas removal vessel and a regeneration vessel.
  • FIG. 3 an arrangement of vessels suitable for use in dehydrating a light hydrocarbon gas stream has been shown, where solid lines represent a launch (new or existing) train and the dotted lines represent possible expansion equipment and associated piping required for a one or two phase expansion.
  • An inlet gas stream is received through line 43 ′ (forty-three prime) and may be passed to dehydration vessels 20 , 21 , 22 , 120 , and 220 that are not in regeneration mode via lines 44 , 45 , 46 , 47 , and 48 respectfully.
  • the product streams, virtually free of water, are recovered through process lines 54 , 55 , 56 , 57 , and 58 respectfully.
  • Each vessel can be designed for operation in either dehydration or regeneration mode, which has not been fully shown for simplicity.
  • vessels 20 and 21 are in dehydration mode while vessel 22 is in regeneration mode where a stripping gas is introduced to vessel 22 via line 70 and exits via line 71 .
  • each vessel is designed with appropriate valves and piping so that all dehydration vessels may operate in either dehydration or regeneration mode, as illustrated through the previous example.
  • cryogenic heat exchangers and associated compressors, turbines, and piping suitable for the liquefaction of a light hydrocarbon gas has been shown where solid lines represent a launch (new or existing) train and the dotted lines represent possible expansion equipment and associated piping required for a one or two phase modular expansion.
  • a gas stream that has been treated in the AGRU and dehydrated is received by process line 59 ′ (fifty-nine prime) and may be distributed to cryogenic heat exchangers 15 , 115 , and 215 via lines 59 , 159 , and 259 respectfully.
  • compressed refrigerant is supplied to cryogenic heat exchangers 15 , 115 , and 215 by turbines 31 , 33 , 35 , 37 , 131 , 135 , 231 , and 235 respectively, which are shaft coupled to refrigerant compressors 32 , 34 , 36 , 38 , 132 , 136 , 232 , and 236 respectfully.
  • High-pressure refrigerant is supplied to compressors 32 , 34 , 132 , and 232 by high-pressure refrigerant lines 61 , 62 , 162 , and 262 .
  • cryogenic heat exchangers 15 , 115 , and 215 typically return high-pressure refrigerant from cryogenic heat exchangers 15 , 115 , and 215 after it has served its purpose as a refrigerant and has been warmed to a substantially gaseous condition.
  • Compressed high-pressure refrigerant is supplied to cryogenic heat exchangers 15 , 115 , and 215 via lines 63 , 64 , 163 , and 263 .
  • Low-pressure refrigerant is supplied to compressors 36 , 38 , 136 , and 236 by low-pressure refrigerant lines 65 , 66 , 166 , and 266 .
  • cryogenic heat exchangers 15 , 115 , and 215 typically return low-pressure refrigerant from cryogenic heat exchangers 15 , 115 , and 215 after it has served its purpose as a refrigerant and has been warmed to substantially gaseous condition.
  • Compressed low-pressure refrigerant is supplied to cryogenic heat exchangers 15 , 115 , and 215 via lines 67 , 68 , 167 , and 267 .
  • refrigerants can be produced from compressors 32 , 34 , 36 , 38 , 132 , 136 , 232 , and 236 at different pressures if desired and passed to cryogenic heat exchangers 15 , 115 , 215 at different points in the refrigeration process if desired and as appropriate.
  • the same or different refrigerants can be used in the high-pressure and low-pressure refrigerant loops.
  • mercury or other contaminant removal equipment is typically employed in a light hydrocarbon liquefaction process.
  • a non-regenerative system or a regenerative system.
  • mercury trapping material such as sulfur, which fixes the volatile mercury in the form of non-volatile mercury sulfide (HgS).
  • HgS non-volatile mercury sulfide
  • an activated carbon is chemically treated or impregnated with a mercury-fixing compound such as sulfur. The mercury is chemi-sorbed onto the non-regenerative carbon, which must be periodically replaced.
  • mercury trapping material such as silver.
  • the silver is supported on alumina or zeolite (mol sieve), or other inert support. This material is placed in the mol sieve unit and the mercury is desorbed during the regeneration cycle.
  • LNG product storage and shipping is also shown in FIG. 4 which includes a LNG product storage facility 361 , which receives product from lines 69 and 69 ′ (sixty-nine prime) as shown. LNG product is then passed from LNG product storage facility 361 via a line 363 to a LNG shipping facility 365 .
  • LNG shipping facility 365 the product LNG is typically shipped, as shown generally by arrow 367 , by sea via a docking, transfer piping and the like to a transport ship, or the product LNG may also be shipped by land pipeline, both as generally known in the art.
  • improved efficiency and economy have been achieved by including in a launch train of a light hydrocarbon gas liquefaction process shared facilities which can be used by subsequent expansions by either modularization or by use of the shared facilities which are designed for the desired maximum capacity of light hydrocarbon gas to be processed in the liquefaction process initially.
  • This results in substantial savings in the overall operation of the process at maximum capacity and provides for great ease in expanding the process incrementally.
  • improved economy can be achieved as discussed by adding a regeneration section which is of a size suitable to regenerate aqueous amine for all of the acid gas removal vessels which are contemplated at maximum capacity of the process comprising all of the trains in combination.
  • the added liquefaction facility can be added with a reduced light hydrocarbon gas flow with a reduced quantity of compressed refrigerant to produce a liquefied light hydrocarbon gas stream in a quantity suitable to meet the current demand.
  • docking facilities, access roads, C 3 + hydrocarbon removal facilities and the like can all be designed for either modular expansion or of a size to accommodate the maximum plant size initially with the resulting efficiency in process expansion when required and economies achieved by reducing the duplication of equipment.

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CN100455960C (zh) 2009-01-28
CA2499578A1 (en) 2004-04-15
BR0306494A (pt) 2004-10-13
US20060112726A1 (en) 2006-06-01
NO20052110L (no) 2005-06-28
EG24009A (en) 2008-03-19
WO2004031670A1 (en) 2004-04-15
JP2011094145A (ja) 2011-05-12
AU2003275396C1 (en) 2010-12-23
US7251956B2 (en) 2007-08-07
AU2003275396A1 (en) 2004-04-23
EP1549893A1 (en) 2005-07-06
NO20052110D0 (no) 2005-04-29
CN1685190A (zh) 2005-10-19
CA2499578C (en) 2012-03-13
US20040118153A1 (en) 2004-06-24
MXPA05003330A (es) 2005-07-05
AU2003275396B2 (en) 2008-02-28
JP2006501434A (ja) 2006-01-12

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